JP2812640B2 - Wastewater treatment device and wastewater treatment method - Google Patents

Wastewater treatment device and wastewater treatment method

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Publication number
JP2812640B2
JP2812640B2 JP14934993A JP14934993A JP2812640B2 JP 2812640 B2 JP2812640 B2 JP 2812640B2 JP 14934993 A JP14934993 A JP 14934993A JP 14934993 A JP14934993 A JP 14934993A JP 2812640 B2 JP2812640 B2 JP 2812640B2
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Prior art keywords
wastewater
water tank
calcium carbonate
carbonate mineral
tank
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Expired - Fee Related
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JP14934993A
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Japanese (ja)
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JPH06343974A (en
Inventor
孝 今井
和之 坂田
和幸 山嵜
重俊 岡谷
憲治 松浦
照朗 永易
喜弘 浜口
博 牧野
憲幸 田中
俊二 細田
聡 西尾
剛 高橋
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シャープ株式会社
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Priority to JP20505692 priority Critical
Priority to JP31339392 priority
Priority to JP3983093 priority
Priority to JP8699693 priority
Priority to JP4-313393 priority
Priority to JP5-39830 priority
Priority to JP5-86996 priority
Priority to JP4-205056 priority
Priority to JP14934993A priority patent/JP2812640B2/en
Application filed by シャープ株式会社 filed Critical シャープ株式会社
Publication of JPH06343974A publication Critical patent/JPH06343974A/en
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/52Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/58Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/583Treatment of water, waste water, or sewage by removing specified dissolved compounds by removing fluoride or fluorine compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/02Aerobic processes
    • C02F3/10Packings; Fillings; Grids
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/10Biological treatment of water, waste water, or sewage
    • Y02W10/15Aerobic processes
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S210/00Liquid purification or separation
    • Y10S210/902Materials removed
    • Y10S210/915Fluorine containing

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wastewater treatment method and a wastewater treatment apparatus capable of effectively treating organic substances such as fluorine and surfactants and hydrogen peroxide in wastewater with a biochemical reaction.

[0002]

2. Description of the Related Art In the recent era of CFC-free, various surfactants, alcohol-based organic solvents, and fluorine-based compounds have been used as substitutes for cleaning CFCs, especially in semiconductor factories and liquid crystal factories, to meet the needs of the era of CFC-free use. Solvents are used. Further, the above-mentioned surfactants, organic solvents, and the like are also used from the direction of miniaturization of the process.

[0003] In particular, cleaning using a combination of ultrapure water and a surfactant is expected as an important alternative cleaning means for realizing complete elimination of CFCs, judging from its cleaning properties and damage to parts. For this reason, with the times, in semiconductor factories and liquid crystal factories, wastewater containing fluorine and a surfactant used in a wafer manufacturing process is increasing.

As a general theory, first, regarding fluorine,
Particularly in the case of a semiconductor factory, the fluorine concentration in the fluorine-containing wastewater is often about 30 to 300 ppm. Then, the influent water containing such a concentration of fluorine is added with chemicals such as slaked lime, polyaluminum chloride, and a polymer flocculant to generate hardly soluble calcium fluoride and aluminum fluoride. Calcium fluoride and aluminum fluoride are made into larger flocs by a flocculant, and the formed flocs are then subjected to wastewater treatment by sedimentation.

On the other hand, with respect to surfactants, in recent semiconductor factories and liquid crystal factories, miniaturization will be further advanced. Becomes difficult to wash. For this reason,
2. Description of the Related Art A method of cleaning a fine portion by reducing the surface tension by mixing a surfactant or an organic substance such as alcohol into ultrapure water is becoming widespread. However, these surfactants and the like are difficult to decompose in microorganisms due to the molecular formula, structural formula, foaming property and bactericidal property of the substance. However, in spite of that, in the future, semiconductor plants and liquid crystal plants are going to be further miniaturized, so that the fluorine-containing wastewater tends to contain a large amount of surfactant and the like in proportion to the miniaturization.
Therefore, simultaneously with the treatment of the fluorine, it is necessary to rationally and economically treat the wastewater containing the organic substance mainly composed of the surfactant.

On the other hand, since ultrapure water containing fluorine also has a cleaning effect on wafers, there is a tendency that fluorine will be contained in wastewater from semiconductor factories and liquid crystal factories. Chemicals used in factories also tend to contain a large amount of surfactants to cope with miniaturization. A typical example of the above chemical is buffered hydrofluoric acid containing a surfactant.

Conventionally, wastewater containing fluorine and a surfactant discharged from various industrial facilities, semiconductor factories, liquid crystal factories and the like has been treated by adding a large amount of slaked lime to the fluorine in the wastewater. While generating hardly soluble calcium fluoride and chemically precipitating and removing the above-mentioned fluorine, for an organic substance such as a surfactant, after the above-mentioned fluorine treatment, a treatment water tank different from the tank for treating fluorine. At the inner,
Microbiological while adding nutrients such as phosphoric acid and urea
There is one that is processed (biologically).

[0008] In a semiconductor factory or a liquid factory that does not have a wastewater treatment facility using microorganisms, organic substances such as surfactants are collected as much as possible in a production process and stored in a tank installed in another place. , A contractor was picked up and processed.

[0009] Conventionally, as an apparatus for treating wastewater containing fluorine and a surfactant, for example, there is an apparatus shown in the system diagram of FIG. FIG. 8 is a system diagram of a two-stage coagulation / sedimentation treatment system including a microorganism treatment. FIG. 7 shows a two-stage coagulation-sedimentation system that does not include a microorganism treatment. The system shown in FIG. 7 is the same as the system shown in FIG. 8 except that the contact oxidation tank 28 is removed.

In FIG. 7, first, the drainage water is supplied to the raw water tank 14.
After being adjusted to a certain amount and quality, the water is transferred to the first reaction tank 15 by the pump 9.

Next, the first reaction tank 15 containing slaked lime is added.
In the above, after the wastewater is stirred and reacted by the stirrer 12 to form calcium fluoride and react with dissolved fluorine, the wastewater is transferred to the second reaction tank 16 to which the aluminum agent has been added, and the stirred reaction treatment is performed. And reacting the fluorine with the unreacted fluorine as aluminum fluoride. In addition, a reaction is performed in which fine flocs of calcium fluoride or aluminum fluoride are wrapped by aluminum hydroxide generated by the addition of the aluminum agent.

Next, the first coagulation tank 17 is provided with the first reaction tank 15.
By adding a polymer flocculant to the fine flocs of calcium fluoride generated by the reaction in the above and the fine flocs of aluminum fluoride generated by the reaction in the second reaction tank 16, a larger floc is formed, First
Solid-liquid separation is performed by the precipitation tank 18. At this time, most of the slurry such as flocs separated into solid and liquid in the first sedimentation tank 18 is hydroxide due to excess slaked lime, and includes reactants such as calcium fluoride and aluminum fluoride. Is less.

Next, in the above process, since the fluorine concentration cannot be reduced below the target water quality of 15 ppm, the waste water is discharged to the third reaction tank 19, the second flocculation tank 20 and the second sedimentation tank 21.
Then, the wastewater is discharged through the PH adjustment tank 22 so that the pH of the wastewater falls within the range of the discharge standard.

The first settling tank 18 and the second settling tank 21
Is collected in the sludge thickening tank 5,
The water is dehydrated by the dehydrator 6 to a cake having a prescribed moisture content.

Next, another conventional example shown in FIG. 8 will be described. In this wastewater treatment apparatus, wastewater containing fluorine and a surfactant first flows into the raw water tank 14. The fluorine-containing wastewater that has flowed into the raw water tank 14 is transferred to the first reaction tank 15 by the raw water tank pump 9 after the amount and quality of the water are adjusted to some extent. Thereafter, slaked lime is added to the fluorine-containing wastewater in the first reaction tank 15, and the fluorine-containing wastewater is stirred and reacted by the stirrer 12. If the reaction time between fluorine and calcium in slaked lime is short, considerable slaked lime is added. Also, when the PH of the fluorine-containing wastewater is very low, considerable slaked lime is added for neutralization.

Next, the waste water is further supplied to the second reaction tank 1.
In step 6, an aluminum agent is added, and unreacted fluorine in the first reaction tank 15 is reacted with aluminum fluoride.

Next, the waste water is reacted in the first coagulation tank 17 with the addition of a polymer coagulant.
The fine flocs of fine calcium fluoride generated by the reaction in step (2) and the fine aluminum fluoride generated by the reaction in the second reaction tank 16 are grown into larger flocs. Then, the waste water is subjected to solid-liquid separation in the first settling tank 18. Most of the sludge such as flocs separated into solid and liquid in the first settling tank 18 is hydroxide derived from excess slaked lime. The above-mentioned sludge includes reactants such as calcium fluoride and aluminum fluoride, but the amount is small and most of the sludge is caused by unreacted chemicals.

Next, the waste water is introduced into a contact oxidation tank 28 filled with a filler 29, and a surfactant is treated by aerobic microorganisms present in the tank 28.
The filler 29 is a corrugated filter made of vinyl chloride or plastic.

However, in this contact oxidation tank 28, even when a nutrient or the like having good culture conditions for microorganisms is added,
Due to the molecular formula, structural formula, bactericidal property and foaming property of the surfactant, the surfactant cannot be easily biodegraded. Therefore, the foaming property remains in the treated water, and it is necessary to newly add an antifoaming agent or the like in order to eliminate the foaming property of the treated water.

Further, the wastewater treatment apparatus includes a first reaction tank 1
Since only the treatment in the first-stage coagulation sedimentation equipment from No. 5 to the first sedimentation tank 18 cannot reduce the fluorine concentration of the treated water to the target water quality of 15 ppm or less, the third reaction tank 1
9, a second-stage coagulation and sedimentation facility including a second coagulation tank 20 and a second sedimentation tank 21.

In the third reaction tank 19, the second precipitation tank 21 is used because of the use of an acidic chemical such as polyaluminum chloride or the reaction time in the third reaction tank 19 is short. In some cases, the pH at the second stage does not fall within the range of the discharge standard.
(PH adjustment tank) 22. In addition, the sludge concentration tank 5
This is a tank for collecting and concentrating sludge from the first settling tank 18 and the second settling tank 21. The sludge concentrated in the sludge concentration tank 5 is dewatered by the dehydrator 6 to a cake having a specified moisture content.

[0022]

Incidentally, the fluorine concentration in the fluorine-containing wastewater of a semiconductor factory is 30 to 300.
Since it fluctuates drastically in the ppm range, the required amount of slaked lime with respect to fluorine in the reaction between fluorine and slaked lime is more than three times the theoretical amount of the chemical reaction as a result.

Further, since the fluorine-containing wastewater in a semiconductor factory is wastewater from a wafer manufacturing process using an acid, the PH is generally low and is in the range of about 2 to 3 in many cases.

For this reason, the wastewater generated in the semiconductor factory contains fluorine, has a low pH, and varies in water quality. Therefore, the amount of the chemical such as slaked lime required for the fluorine treatment and the neutralization reaction is used. There are many. As a result, the amount of waste such as dehydrated cake finally discharged becomes large, and there is a problem that not only disposal costs but also security of a future waste disposal site is uncertain. That is, a large amount of cake is dehydrated by the dehydrator 6 and the large amount of dewatered cake is landfilled as industrial waste. In other words, a large amount of wastewater containing organic substances such as fluorine and surfactants is generated from semiconductor factories and liquid crystal factories. It is becoming. The industrial waste generated from these semiconductor factories and liquid crystal factories is steadily increasing, and measures for increasing waste, including securing of disposal sites, are urgently needed.

The above problem will be repeatedly described below. In the conventional method for treating fluorine by adding slaked lime, etc., the PH of the fluorine-containing wastewater is low and the fluorine concentration of the fluorine-containing wastewater fluctuates drastically, so the amount of slaked lime required for the neutralization reaction is properly controlled. And it is difficult to control the reaction. Therefore, as a result, excess slaked lime is required. Generally, in a semiconductor factory, slaked lime is added to the amount of fluorine three times or more of the theoretical amount of the chemical reaction as described above with respect to the amount of fluorine. Since slaked lime is added three times or more, the amount of unreacted calcium increases, and the amount of sludge such as hydroxide increases. And even if the above-mentioned sludge is dehydrated by a dehydrator such as a filter press, the water content is 65%.
As a result, the volume of the dehydrated cake was increased as a result. On the other hand, the required amount of slaked lime
Another reason that the theoretical amount is three times or more is that the reaction time between the fluorine-containing waste water and the slaked lime to be added is generally designed within 30 minutes. Cannot be secured, and the target value for the first stage coagulation sedimentation
(Generally 20 to 30 ppm). Conversely, if the reaction time is designed to be long enough, the capacity of the reaction tank must be increased three times or more, and the stirrer must be larger, so that the site area and construction costs are reduced. Is not rational and not economic.

Further, the treatment of the surfactant has a technical problem that it is difficult to treat the surfactant with microorganisms, particularly since the surfactant has bactericidal properties against microorganisms.

On the other hand, regulations on the concentration of fluorine in the treated water are becoming stricter year by year. In recent plants, the regulated value of fluorine in consideration of administrative standards is often as low as several ppm, and is one digit. In order to maintain the concentration, it was impossible to reduce the fluorine concentration to a target fluorine concentration in an actual device unless the aluminum agent was added at least 10 times the fluorine concentration. Further, as shown in FIG. 7, in a wastewater treatment apparatus having no contact oxidation tank 28, wastewater containing an organic substance such as the above-mentioned surfactant cannot be treated with microorganisms.
There is a problem that the quality of the effluent, especially D, deteriorates.

On the other hand, today, the rational and economical treatment of wastewater and the reduction of waste are social needs.
And they are important from the viewpoint of protecting the global environment,
In particular, ensuring the quality of treated water from semiconductor factories and liquid crystal factories and reducing waste are urgent issues to be resolved immediately.

By the way, conventionally, the wastewater containing fluorine and the wastewater containing hydrogen peroxide are separately treated. The reason is that if hydrogen peroxide is mixed in the fluorine-containing wastewater, it will adversely affect the function of coagulation and sedimentation,
Furthermore, hydrogen peroxide itself becomes a COD source and raises the COD value of the effluent.

That is, for the wastewater containing the above-mentioned hydrogen peroxide solution, for example, a peroxide (hydrogen peroxide solution) decomposition chemical
(For example, a cliverter (trade name)) was added to perform wastewater treatment. Alternatively, for example, permeate-containing wastewater having a permeate concentration of 1000 ppm or less is introduced into a permeate raw water tank 55 as shown in FIG. It is transferred to the packed perhydrolysis tower 56. And
In the perhydrolysis tower 56, the permeate-containing wastewater was decomposed into water and oxygen gas using activated carbon as a catalyst, and after decomposition, introduced into a permeated water tank 57 and subjected to wastewater treatment.

However, when the pipes are separated in the production process for discharging fluorine and hydrogen peroxide, due to the large number of production equipment and the complicated structure of the production equipment itself, the hydrogen Since it is difficult to reliably prevent the wastewater from being contained in the contained wastewater, a wastewater treatment apparatus capable of treating wastewater containing excess water and fluorine with one apparatus is desired.

In the conventional example, the raw water tank 14 is a tank for adjusting only the amount of water, and has a large tank capacity in relation to the residence time, but has no function of reacting with fluorine. No, from an investment efficiency standpoint, it was not an effective tank. Therefore, it is desired to design the raw water tank effectively with respect to the treatment of wastewater and improve the investment efficiency.

In a semiconductor factory, a liquid crystal factory, and the like, there is always domestic wastewater from a cafeteria, a bath, a toilet, and the like used by employees, and a domestic wastewater treatment facility for treating such domestic wastewater supplies nutrients. A well-balanced surplus sludge was generated, and this surplus sludge was not disposed of at a semiconductor plant or a liquid crystal plant, but had to be disposed of at a cost.

Accordingly, an object of the present invention is to provide a reasonable and economical wastewater treatment system which has a small amount of waste, has excellent treatment water quality with respect to wastewater containing organic substances such as surfactants, and has a low construction cost. It is to provide a method and a wastewater treatment device. Another object of the present invention is to provide means for reducing the cost of treating wastewater containing fluorine and surfactants, reducing the generation of dewatered cake, and also treating surplus sludge for domestic use. It is another object of the present invention to provide a wastewater treatment apparatus and a wastewater treatment method that can simultaneously treat wastewater containing both fluorine and superhydrogen.

[0035]

The wastewater treatment apparatus according to the present invention has a means for introducing wastewater containing fluorine and a means for stirring, and a first water tank filled with calcium carbonate mineral. And a means for introducing wastewater treated by the first water tank and a means for stirring, wherein an aluminum agent is added, and the second is filled with a calcium carbonate mineral.
A wastewater treatment device comprising a water tank.

In the wastewater treatment method of the present invention, the wastewater containing calcium is reacted with the calcium carbonate in the first water tank filled with the calcium carbonate mineral while stirring the wastewater containing fluorine. A step of reducing the fluorine concentration of the wastewater to a predetermined value; and, while stirring the wastewater treated in the step, an aluminum agent is added, and the wastewater is drained in the second water tank filled with calcium carbonate mineral. And a step of reacting with an aluminum agent and a calcium carbonate mineral to reduce the fluorine concentration of the wastewater to a predetermined value and to adjust PH to a value within a predetermined range.

According to a third aspect of the present invention, there is provided a wastewater treatment apparatus comprising a means for introducing wastewater containing fluorine and an organic substance and a means for stirring, a first water tank filled with calcium carbonate mineral, It has a means for introducing wastewater treated by the first water tank and a means for stirring, a second water tank to which an aluminum agent is added and filled with calcium carbonate mineral, and a wastewater treated by the second water tank. A third water tank having a means for introducing and stirring means, and a polymer coagulant added thereto, and a fourth water tank having means for separating wastewater from the third water tank into solid and liquid and discharging the overhead liquid. A wastewater treatment apparatus, comprising: a fifth water tank that sediments sediment formed in the fourth water tank by sedimentation and separation, and a dewatering device that dewaters the sludge concentrated in the fifth water tank. It is.

In the wastewater treatment method according to the present invention, the wastewater containing fluorine and an organic substance is stirred while stirring.
In the first water tank filled with the calcium carbonate mineral, a step of reacting the wastewater with calcium carbonate to reduce the fluorine concentration of the wastewater to a predetermined value, and while stirring the wastewater treated in the step, In the second water tank to which the aluminum agent is added and the calcium carbonate mineral is filled, the wastewater is reacted with the aluminum agent and the calcium carbonate mineral to reduce the fluorine concentration of the wastewater to a predetermined value, and to adjust the PH to a predetermined range. , A step of concentrating the sludge generated in the step by sedimentation and separation, and a step of dewatering the sludge concentrated in the step.

A wastewater treatment apparatus according to a fifth aspect of the present invention comprises a sixth water tank having means for introducing wastewater from the second water tank and leading the wastewater to the third water tank and sludge fixing means. 4. The wastewater treatment apparatus according to claim 3, further comprising a conveying unit configured to convey the sludge settled and formed in the fourth water tank to the fifth water tank or the sixth water tank.

[0040] The wastewater treatment apparatus according to the present invention according to claim 6, further comprising means for introducing Bacillus subtilis kubota bacteria into the sixth water tank. is there.

The wastewater treatment apparatus of the present invention according to claim 7, further comprising means for introducing the Bacillus subtilis kubota bacterium and surplus sludge for domestic use into the sixth water tank. A wastewater treatment device according to item 1.

[0042] In the wastewater treatment apparatus according to the present invention, the stirring means provided in the first water tank is aeration stirring using air containing ozone, and the wastewater treatment apparatus is provided in the second water tank. The wastewater treatment apparatus according to any one of claims 1, 3, 5, 6, and 7, wherein the means for stirring is aeration with air containing no ozone.

Further, the invention according to claim 9 is a wastewater introduction means for introducing wastewater, a stirring means for stirring the wastewater and adjusting the stirring power to be strong or weak, and a filling means filled with calcium carbonate mineral. A first water tank having a portion, a wastewater introduction means for introducing wastewater from the first water tank, a stirring means for stirring the wastewater and adjusting the stirring power to be strong and weak, and a calcium carbonate mineral. A second water tank to which an aluminum agent is added having a filling portion.

The invention according to claim 10 is a step of introducing wastewater into a first water tank filled with a calcium carbonate mineral, and reacting the wastewater with the calcium carbonate mineral in the first water tank. Reducing the fluorine concentration of the wastewater to a predetermined value, and draining the wastewater from the first water tank,
Introducing the aluminum agent and the calcium carbonate mineral into the second water tank filled with the calcium carbonate mineral, and adding an aluminum agent while stirring the wastewater in the second water tank; and mixing the aluminum agent and the calcium carbonate mineral in the second water tank. And the above-mentioned waste water, and
The microorganisms that peel off from the calcium carbonate mineral when the calcium carbonate mineral is aerated are allowed to react with the wastewater, and further, the reaction products are aggregated, and the fluorine concentration and the hydrogen peroxide concentration of the wastewater are set to predetermined values. And adjusting the pH value of the wastewater to a value within a predetermined range.

According to an eleventh aspect of the present invention, in the effluent treatment apparatus according to the ninth aspect, the first water tank and the second water tank include a perforated plate for partitioning an inner space of the pipe into an upper part and a lower part. It has a mesh tube whose wall is meshed,
The upper space of the mesh tube is filled with a calcium carbonate mineral, and the lower space of the mesh tube is an unfilled air reservoir.

According to a twelfth aspect of the present invention, in the effluent treatment apparatus according to the ninth aspect, the stirring means includes an aeration means including a diffuser tube.

According to a thirteenth aspect of the present invention, there is provided the drainage treatment device according to the twelfth aspect, wherein a PH meter for measuring a PH value of the wastewater introduced from the first water tank to the second water tank, and a fluorine meter for the wastewater. Having a fluorine concentration meter for measuring the concentration,
An aeration output control means for controlling the aeration output of the aeration means of the stirring means based on the PH value measured by the PH meter and the fluorine concentration measured by the fluorine concentration meter.

Further, the invention according to claim 14 is a wastewater introducing means for introducing wastewater, a stirring means for stirring the wastewater and adjusting the stirring power to be strong or weak, and a filling means filled with calcium carbonate mineral. A first water tank having a portion, a wastewater introduction means for introducing wastewater from the first water tank, a stirring means for stirring the wastewater and adjusting the stirring power to be strong and weak, and a calcium carbonate mineral and activated carbon filling. And a second water tank to which an aluminum agent is added.

Further, the invention according to claim 15 is a step of introducing wastewater into a first water tank filled with a calcium carbonate mineral, and reacting the wastewater with the calcium carbonate mineral in the first water tank. Reducing the fluorine concentration of the wastewater to a predetermined value, and draining the wastewater from the first water tank,
Introducing the aluminum agent into the second water tank filled with the calcium carbonate mineral and the activated carbon, and adding an aluminum agent while stirring the wastewater in the second water tank; A calcium mineral and the activated carbon,
The wastewater is reacted with, and, when the calcium carbonate mineral and the activated carbon are aerated, the microorganisms that peel off from the calcium carbonate mineral and the activated carbon are reacted with the wastewater, and further, the reaction product is agglomerated. Reducing the concentration of fluorine and the concentration of hydrogen peroxide in the wastewater to predetermined values, and setting the PH value of the wastewater to a value in a predetermined range.

According to a sixteenth aspect of the present invention, in the wastewater treatment apparatus according to the sixteenth aspect, the first water tank and the second water tank include a perforated plate for partitioning an inner space of the pipe into an upper part and a lower part. The first water tank has a net-like tube having a mesh-like wall, the upper space of the mesh-like tube of the first water tank is filled with calcium carbonate mineral, and the lower space of the mesh-like tube is an unfilled air reservoir. The upper space of the mesh tube of the second water tank is filled with a calcium carbonate mineral and activated carbon, and the lower space of the mesh tube is an unfilled air reservoir. Features.

According to a seventeenth aspect of the present invention, in the wastewater treatment apparatus according to the sixteenth aspect, the stirring means comprises:
It is characterized by including aeration means including a diffuser tube.

The invention according to claim 18 is the drainage treatment device according to claim 19, wherein the PH meter for measuring the PH value of the wastewater introduced from the first water tank to the second water tank and the fluorine meter for the wastewater. Having a fluorine concentration meter for measuring the concentration,
An aeration output control means for controlling the aeration output of the aeration means of the stirring means based on the PH value measured by the PH meter and the fluorine concentration measured by the fluorine concentration meter.

[0053]

According to the present invention described in claims 1 to 4,
After removing the fluorine and organic matter contained in the wastewater, a less dehydrated cake is formed than before.

Further, when the present invention according to claim 5 is used, the sludge from the fourth water tank is fixed to the sixth water tank by the sludge fixing means in the sixth water tank, and the microorganisms existing in the sixth water tank are fixed. Is cultured to perform a higher treatment of organic substances than before.

Further, when the present invention according to claim 6 is used, it is possible to perform a higher treatment of organic substances than the present invention according to claim 5 by BSK bacteria cultured using surplus sludge as a nutrient. it can.

When the present invention according to claim 7 is used, surplus sludge in living systems is treated with BSK bacteria, and the BSK bacteria obtain nutrients and propagate more. Sludge from the fourth tank can be treated at a high level.

Further, when the present invention according to claim 8 is used, an organic substance contained in waste water is oxidized and decomposed by ozone, and at the same time, it acts as a catalyst for promoting the reaction between fluorine and calcium carbonate mineral, and Oxidative decolorization occurs when the wastewater is colored by the incorporation of resist or the like.

The wastewater treatment apparatus according to the ninth aspect of the present invention
It has a wastewater introduction means for introducing wastewater and a stirring means whose stirring intensity can be adjusted, and has a first water tank having a filling portion pre-filled with a calcium carbonate mineral, so that the fluorine contained in the wastewater and the calcium carbonate are contained. The minerals react with each other to treat the fluorine in the wastewater. Further, since the crystalline reactant of calcium fluoride generated on the surface of the calcium carbonate mineral is separated from the surface of the calcium carbonate mineral by the stirring of the stirring means, the reaction between the calcium carbonate mineral and the fluorine is performed. Is promoted, and the fluorine treatment is efficiently performed. In addition, since microorganisms are easily generated on the surface of the calcium carbonate mineral, the calcium carbonate mineral serves as a carrier for immobilizing the microorganism. Then, the microorganisms eat fluorine in the wastewater and concentrate in the body. In particular, when a microorganism having a remarkable ability to accumulate fluorine in the body is found in the future, by utilizing the microorganism, the processing ability of fluorine is remarkably improved.

Further, the wastewater treatment apparatus according to claim 9 is
Further, in the second water tank, an aluminum agent is added to the wastewater, and the aluminum agent reacts with fluorine contained in the wastewater to produce aluminum fluoride. In addition, aluminum hydroxide is generated from the aluminum agent, and the aluminum hydroxide is flocculated, and the aluminum fluoride floc is adsorbed on the aluminum hydroxide floc by the adsorption action of the aluminum hydroxide floc. Also in this second water tank, the treatment of fluorine by the calcium carbonate mineral and the microorganisms inhabiting the calcium carbonate mineral further proceeds.

According to the wastewater treatment method of the present invention, the wastewater treatment is performed, the fluorine concentration of the wastewater is reduced to a predetermined value, and the PH value of the wastewater is reduced.
The value is set within a predetermined range close to neutrality.

Further, according to the wastewater treatment apparatus of the present invention, there is provided a reticulated pipe for storing the calcium carbonate mineral, and the lower part of the reticulated pipe is an unfilled air reservoir. If air is supplied from below, the calcium carbonate mineral is efficiently supplied with air. Therefore, microorganisms derived from the air easily grow on the calcium carbonate mineral, and the efficiency of wastewater treatment by the microorganisms is improved.

According to the twelfth aspect of the present invention,
Since the stirring means includes aeration means including a diffuser tube, the supply of air from the diffuser tube agitates drainage in a water tank provided with the mesh pipe, and makes the inside of the tank aerobic. Therefore, the aerobic microorganisms can easily treat the organic matter in the wastewater, and the efficiency of the wastewater treatment is improved.

The wastewater treatment apparatus according to the thirteenth aspect measures the PH value of the wastewater and the fluorine concentration of the wastewater, and outputs the aeration output of the stirring means based on the PH value and the fluorine concentration. , The wastewater treatment capacity is optimally controlled according to the wastewater.

According to the wastewater treatment apparatus of the invention, the second water tank is filled with activated carbon in addition to the calcium carbonate mineral. In addition, the activated carbon has an action of decomposing hydrogen peroxide in wastewater. Therefore, according to the invention of claim 15, waste water containing fluorine and hydrogen peroxide is simultaneously treated.

According to the wastewater treatment method of the present invention, the calcium carbonate mineral and the aluminum agent treat fluorine in the wastewater, and the activated carbon removes hydrogen peroxide in the wastewater. After the treatment, the fluorine concentration and the hydrogen peroxide concentration in the wastewater are reduced to predetermined values, and the PH value in the wastewater is set to a value in a predetermined range.

Further, in the wastewater treatment apparatus according to the present invention, the first water tank has a mesh tube filled with calcium carbonate mineral, and the second water tank has a mesh tube filled with calcium carbonate mineral and activated carbon. Since the lower space of the mesh tube is a non-filled air reservoir, the air is efficiently supplied to the calcium carbonate mineral by supplying air from the lower portion of the mesh tube. Therefore, microorganisms derived from the air easily grow on the calcium carbonate mineral, and the efficiency of wastewater treatment by the microorganisms is improved. Further, in the second water tank, air is efficiently supplied not only to the calcium carbonate mineral but also to the activated carbon, so that microorganisms derived from air easily propagate in the activated carbon, and the efficiency of wastewater treatment by microorganisms is reduced. Be improved.

Further, in the wastewater treatment apparatus according to the present invention, since the stirring means includes aeration means including an air diffuser, the water tank provided with the mesh pipe is supplied by the supply of air from the air diffuser. The internal drainage is stirred, and the inside of the tank becomes aerobic. Therefore, the aerobic microorganisms can easily treat the organic matter in the wastewater, and the efficiency of the wastewater treatment is improved.

Further, according to the waste water treatment apparatus of the invention, the PH value of the waste water and the fluorine concentration of the waste water are measured, and based on the PH value and the fluorine concentration, the agitation means of the stirring means is measured. Since the aeration output is controlled, according to the above drainage,
Wastewater treatment capacity is optimally controlled.

According to the effluent treatment apparatus of the ninth aspect or the effluent treatment method of the tenth aspect, the fluorine concentration of the fluorine-containing wastewater in the first water tank is 15 to 20.
It can be reduced to ppm and the pH approaches 7. In the first water tank, water, carbon dioxide gas, and calcium fluoride as a precipitate are generated.

Further, in the second water tank, the fluorine concentration becomes about 3 ppm, and the PH further approaches 7. Also,
Aluminum hydroxide is generated from the aluminum agent, and aluminum fluoride generated in the second water tank is adsorbed on the aluminum hydroxide by the adsorption action of the aluminum hydroxide floc.

Further, according to the invention of the fourteenth and fifteenth aspects, the microorganisms mixed from the air on the surfaces of the calcium carbonate mineral and the activated carbon filled in the first and second water tanks propagate or The microorganisms added to the aquarium proliferate over time, and then the wastewater approaches neutrality due to the buffering action of the microorganisms, and biological organisms are treated by the microorganisms. Then, when the microorganisms are peeled off from the calcium carbonate mineral and the activated carbon by strong aeration, the microorganisms exhibit microbial cohesiveness. On the other hand, as described above, the microorganisms immobilized on the calcium carbonate mineral and the activated carbon are in a normal state,
It also has the effect of taking fluorine into the body.

Here, aluminum hydroxide is a substance that is generated even in a water purification plant due to the addition of an aluminum agent, but is also a substance that is relatively chemically friendly to fish including microorganisms. Has little effect on microbial activity.

Further, the following relates to the fluorine treatment in the above-mentioned fluorine-containing waste water.
Differences from the invention described in claims 9 to 18 will be described. Conventionally, for example, there has been a method of treating fluorine by attaching calcium carbonate instead of slaked lime (Japanese Patent Publication No.
10120). However, although this conventional example has a common feature with the above-mentioned invention in using calcium carbonate, the conventional method merely adds calcium carbonate to a reaction tank having a short residence time, and as a result, unreacted There is a disadvantage that calcium carbonate is also generated and a large amount of sludge is generated. On the other hand, the present invention does not add calcium carbonate, but specifically, for example, fills the first water tank with calcium carbonate minerals for several months in advance and advances the reaction to fluorine by aeration. Thus, the reaction with fluorine was reliably carried out according to the chemical formula, and according to the operation test results for about six months, the amount of generated sludge was extremely small as compared with the conventional example. Conventionally, there has been a method of simply adding calcium carbonate to a reaction tank.However, the present invention has a unique function having both a function of adjusting water quality and a function of reacting fluorine and calcium in wastewater and resulting neutralization. Since the first and second water tanks serving as reaction adjustment tanks are provided, the method is fundamentally different from the above-described method of simply adding calcium carbonate, and the treatment capacity of wastewater containing fluorine is remarkably excellent. is there.

Conventionally, there has been a processing method in which an aluminum agent is simply added. However, in a processing method in which an aluminum agent is simply added, an excessive aluminum agent is not added to the treatment of fluorine. The disadvantage is that the amount of chemicals used as an aluminum agent is large because the concentration of fluorine and fluorine does not decrease
(See JP-A-51-3260). On the other hand, in the present invention, since the calcium carbonate mineral and the activated carbon are filled in the tank, the calcium carbonate mineral and the activated carbon are strongly aerated or agitated in the tank so that the microorganisms can be separated from the calcium carbonate mineral and the activated carbon. Can be used to take advantage of the cohesiveness of naturally occurring microorganisms (activated sludge also has some cohesiveness, but the same content). In other words, according to the present invention, fluorine, which is a non-processed material, is agglomerated, so that fluorine can be effectively processed by adding a small amount of an aluminum agent. Therefore, according to the present invention, the amount of the aluminum agent used can be reduced as compared with the conventional method. In addition, when it is necessary to propagate a lot of microorganisms, surplus sludge from living
The microorganisms resulting from the surplus sludge of the living system may be immobilized on the surface of the calcium carbonate mineral and the activated carbon by adding to the water tank. Further, the surplus sludge of the living system may be constantly added to the second water tank. And it is empirical that when the wastewater is sufficiently aerated, the fluorine treatment effect of the aluminum agent can be improved and the amount of the aluminum agent added can be reduced. In any case, the present invention is fundamentally different from the prior art in that microorganisms are used for treating fluorine.

[0075]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the illustrated embodiments.

FIG. 1 shows a wastewater containing fluorine or fluorine and an organic substance according to one embodiment of the present invention.
FIG. 2 is a conceptual diagram of a wastewater treatment apparatus according to one embodiment of the present invention,
FIG. 3 shows a wastewater treatment apparatus according to one embodiment of the present invention. FIG. 4 shows a wastewater treatment apparatus according to one embodiment of the present invention.

1 to 4, reference numeral 1 denotes a first reaction adjusting tank, which is filled with a calcium carbonate mineral 7, and is used for connecting a blower 10, an air diffuser 8 and the blower 10 to the air diffuser 8. Although an aeration device including the piping 11 is provided, a mechanical stirrer 12 can be applied instead of the aeration device as shown in FIG. The water level of the first reaction adjustment tank 1 is adjusted so that the calcium carbonate mineral 7 is buried therein, and is 50% of the capacity of the first reaction adjustment tank 1.
The degree is used for adjusting the amount of water. Reference numeral 2 denotes a second reaction adjusting tank, which is filled with a calcium carbonate mineral 7.
In addition, an aluminum agent (not shown) is added, and an aeration device similar to that of the first reaction adjustment tank 1 is provided.

The calcium carbonate mineral 7 used in Examples 1 to 4 of the present invention is obtained by pulverizing natural limestone, and also exists as a product called heavy calcium carbonate or cold water stone. Also, while slaked lime is a strong alkali, it is a chemically safe substance that can breed small fish in a naturally-occurring aqueous solution of calcium carbonate minerals. Easy to breed.

The particle size of the calcium carbonate mineral 7 filled in the first reaction adjusting tank 1 is determined by the pH of the wastewater immediately after inflow.
Is less than or equal to 3 and it is better that the particle size is coarse. Therefore, the calcium carbonate mineral 7 filled in the second reaction adjusting tank 2
For example, the calcium carbonate mineral in the first reaction adjusting tank 1 has a diameter of about 5 to 7 cm, and the calcium carbonate mineral in the second reaction adjusting tank 2 has a diameter of about 2 cm. , Not an absolute condition.

Further, the aluminum agent has a fluorine concentration of 15 to 2
0 ppm or less, and more near neutral, fluorine is effectively removed, so in the first reaction adjustment tank 1,
First, the calcium carbonate mineral 7 is used to reduce the fluorine concentration to 15%.
The concentration of fluorine is reduced to about 5 ppm by using an aluminum agent in order to perform a higher degree of fluorine removal in the second reaction adjusting tank 2 by setting the pH to about 20 ppm and bringing the PH closer to 7.

Further, 3 is a flocculation tank, 4 is a first sedimentation tank, 5 is a sludge condensing tank, 6 is a dehydrator, 12 is a stirrer, 13 is a scraper, and 24 is a cord-like contact material made of vinylidene chloride (hereinafter referred to as a contact material). , “Contact material”), 25 is a BSK bacteria culture tank, 2
6 is a sludge microorganism mixing tank, 27 is a heating device, 30 is an ozone generator, 31 is a filter, 32 is an ozone mixing section, 33
Indicates a packing.

In the wastewater treatment apparatus according to the first and third aspects of the present invention, the conventional raw water tank 14 is filled with the calcium carbonate mineral 7, and the agitating means is an aeration apparatus or a mechanical stirring apparatus. And the process of reducing the concentration of fluorine in the wastewater can be performed by neutralizing the wastewater and reacting the fluorine contained in the wastewater with calcium carbonate, so that the scale of the wastewater treatment device is smaller than before. .

As the agitating means, an aeration apparatus is more aerobic with aerated air, so that microorganisms are more likely to be mixed into wastewater, and are more suitable.

The wastewater treatment apparatus according to the present invention is provided with a sludge fixing tank 23 into which wastewater from the second reaction adjusting tank 2 and sludge from the sedimentation tank 4 flow. The tank 23 is filled with a contact material 24 for fixing the sludge returned from the settling tank 4. In addition, as the material of the contact material 24, any material that is lightweight, has corrosion resistance, alkali resistance, and acid resistance in addition to vinylidene chloride can be used, and the contact area with sludge should be as large as possible. Good. Specifically, it is possible to use a cord-like product having a number of radial ring-shaped elements of vinylidene chloride.

In the wastewater treatment apparatus according to the present invention, a heating device 27 is provided, and BSK is provided.
BSK bacterium cultivation tank 25 filled with germs or BSK bacterium and surplus sludge for daily living which is a nutrient of BSK bacterium and BSK
A sludge microorganism mixing tank 26 for mixing the BSK bacteria from the bacteria culture tank 25 and the sludge from the sedimentation tank 4 and transporting the mixture to the sludge immobilization tank 23 is provided. In addition, BSK bacteria
It is an aerobic microorganism and is a kind of Bacillus subtilis, like Bacillus natto, which exists in nature. It has a high deodorizing ability against odors and effectively deodorizes odors generated by surplus sludge from daily life.

Further, in the wastewater treatment apparatus according to the present invention, a filter 31 and an ozone generator 30 for removing dirt from the air are provided in the middle of the air pipe from the blower 10 to the exhaust pipe 8. The air containing ozone is discharged from the air diffuser 8. And, in order to dissolve ozone more in water, a ceramic or plastic filler 33 used for a scrubber or the like used for an exhaust treatment,
Specifically, a Raschig ring, a Berl saddle, an interlock saddle, a terraret, a pole ring, and the like are filled in the ozone mixing unit 32 to improve the gas-liquid reaction efficiency.

It is more effective that the amount of generated ozone is 20 mg / H or more per 1 M 3 of wastewater. However, the optimum value is determined in advance by determining the amount of generated ozone from the fluorine concentration and COD concentration of the treated water by experiments. I just need. (Embodiment 1) Next, a wastewater treatment step according to one embodiment of the present invention will be described with reference to FIG.

First, waste water containing fluorine and a surfactant (hereinafter referred to as “waste water”) is transferred to the first reaction adjusting tank 1.
Here, the amount of water is adjusted so that the calcium carbonate mineral 7 is buried, fluorine is removed and neutralized by the calcium carbonate mineral 7, and the fluorine concentration is 15 to 20 ppm and the PH is 4 to 5. The water temperature at the time of the treatment may be 20 ° C. or higher, but 25 ° C. or higher is effective.
It is desirable to plan in the first half of the wastewater treatment facilities.
The reaction time in the first reaction control tank 1 is determined by the concentration of fluorine contained in the wastewater, the inflow amount of the wastewater and the quality of the inflow water, but is considerably longer than in the past, and is usually 12 hours or more. I do. At the time of the aeration and stirring, microorganisms existing in the air are mixed into the wastewater, propagate on the surface of the calcium carbonate mineral 7, and the wastewater approaches neutrality due to the buffering action of the microorganisms. In addition, it is preferable to design the amount of air in the air aeration at 20 M 3 or more per day per 1 M 3 of water tank capacity.

The waste water immediately after flowing into the first reaction control tank 1 is P
Since H is acidic of 3 or less, calcium is ionized while dissolving the calcium carbonate mineral 7, and the fluorine is treated as fine flocs of calcium fluoride,
Along with that, carbon dioxide gas and water are generated. Conventionally, hydroxide was generated because excess slaked lime (Ca (OH) 2 ) was added, but in the present invention, the first reaction adjusting tank 1
In the above, the reaction with calcium carbonate is performed over a sufficient time according to the chemical reaction formula, so that the above-mentioned hydroxide is not generated, the amount of dehydrated cake produced is reduced, and the fluorine contained in the wastewater is reduced by 60%. % Or more can be removed.

On the other hand, as a part of the reaction, a phenomenon occurs in which dissolved fluorine reacts with the calcium carbonate mineral 7 and changes into a calcium fluoride mineral (fluorite). This phenomenon tends to change to calcium fluoride minerals rather than becoming fine calcium fluoride precipitates as the fluorine concentration in the wastewater is higher. This fluorite can be reused as a raw material for producing fluorine in a cycle of fluorite → hydrofluoric acid → purified hydrofluoric acid → used in IC factories → drainage → fluorite. The change to the calcium fluoride mineral also occurs in the first reaction adjustment tank 1 of Examples 2 to 4 described below.

Next, the waste water having a fluorine concentration of 15 to 20 ppm and approaching neutrality is transferred to the second reaction adjusting tank 2, where polyaluminum chloride as an aluminum agent and aluminum sulfate called a sulfuric acid band are removed. 500-1000pp
About m is added. In addition, it is preferable to set residence time to 6 hours or more. This aluminum agent reacts with the fluorine contained in the wastewater to form aluminum fluoride, and the excess aluminum agent quickly changes into a floc of aluminum hydroxide and absorbs the aluminum fluoride, thereby reducing the fluorine concentration in the wastewater. Reduce to about 5 ppm. It is known that this aluminum hydroxide floc is likely to be generated near neutrality.

However, the pH of the waste water is lowered by the addition of the acidic agent as the above-mentioned aluminum agent. Therefore, conventionally, an alkaline agent such as caustic soda is added to neutralize the wastewater. By filling the calcium carbonate mineral 7 in the first reaction adjustment tank 1 and the second reaction adjustment tank 2,
Neutralization by the calcium carbonate mineral 7 and neutralization by microorganisms from the air that propagate on the surface of the calcium carbonate mineral are automatically and safely performed, and the PH is adjusted to about 5.8 to 8.6. For this reason, the conventionally required PH adjustment tank is not required.

As described above, in the second reaction adjusting tank 2, the fluorine contained in the wastewater can be removed by 60% or more, and when organic substances such as surfactants are taken as COD (Chemical Oxygen Demand), the removal rate is 40%. The above can be expected.

Next, the waste water is transferred to the coagulation tank 3, and the fine flocs generated in the first and second reaction control tanks 1 and 2 are added to the polymer coagulant by about several ppm to make them large and firm. Grow to flock. The stirring in the flocculation tank 3 is performed so as not to break the floc.
Slow mechanical agitation is suitable. The reaction time may be about 15 minutes.

Next, the waste water is transferred to the sedimentation tank 4 and subjected to solid-liquid separation using the scraper 13 at a rotational speed of about once every several minutes, and the waste water as a supernatant liquid is discharged to form a precipitate. The sludge is gathered in the sludge thickening tank 5 using the scraper 13, concentrated by sedimentation for 3 hours or more, and then the sludge concentrated by the above treatment is dewatered by the dehydrator 6 such as a filter press. Produce dewatered cake as waste. (Embodiment 2) Next, a wastewater treatment step according to an embodiment of the present invention will be described with reference to FIG.

First, the waste water is transferred to the first reaction adjusting tank 1 as in Example 1, and the calcium carbonate mineral 7 is used to remove and neutralize fluorine. For example, when the amount of air used for air aeration is 20 M 3 or more per day for 1 M 3 of water tank capacity, the influent with a fluorine concentration of 100 ppm and a pH of 2.5 is 40 ppm or less at the outlet of the first reaction adjustment tank 1. , PH 4-5
Becomes

Next, wastewater having a fluorine concentration of 40 ppm
It is transferred to the second reaction adjustment tank 2 and polyaluminum chloride as an aluminum agent or aluminum sulfate called a sulfuric acid band is added, and the fluorine concentration of the wastewater is reduced to about 16 ppm, and the PH becomes 5 to 7.

Next, the waste water is transferred to the coagulation tank 3 via the sludge immobilization tank 23, and the fine flocs generated in the first and second reaction adjustment tanks 1 and 2 are removed by the polymer coagulant. To grow into large and solid flocks.

Next, the waste water was transferred to the sedimentation tank 4 and subjected to solid-liquid separation using the scraper 13 at a rotation speed of about once every several minutes, and the waste water as a supernatant liquid was discharged to form a precipitate. Unreacted sludge containing aluminum, calcium and fluorine is returned to the sludge fixing tank 23.

The sludge return rate is initially set to 100%. However, when the sludge concentration in the sludge fixing tank 23 becomes 3000 ppm or more, in the 100% sludge return rate operation, the wastewater in the flocculation tank 3 and the wastewater in the sedimentation tank 4 are removed. Since sludge is mixed in the supernatant, the sludge return rate is reduced to a range where sludge is not mixed in the drainage in the flocculation tank 3 and the supernatant in the sedimentation tank 4. At this time, 30% or more of the sludge is adhered and fixed to the contact material 24, anaerobic microorganisms propagate in gaps existing in the contact material 24, digest the sludge, and reduce the amount of sludge.

The removal rate of fluorine in the sludge fixing tank 23 can be expected to be 60% or more, and the removal rate when organic substances such as surfactants are taken as COD can be expected to be 40% or more.

Next, as in the first embodiment, the sludge is concentrated in the sludge concentration tank 5 and dewatered by the dehydrator 6 to form a dewatered cake.

As described above, if the processing step of Example 2 is used, for example, the first reaction adjustment tank 1 having a capacity of about 5 liters,
When the above steps were carried out using a 2 liter second reaction adjustment tank 2, a sludge immobilization tank 23 having a capacity of about 2.5 liters, and a sedimentation tank 4 having a capacity of about 3 liters, the pH was 2.4 and the fluorine was 2.4. When treating wastewater containing fluorine and a surfactant having a concentration of 135 ppm and a COD of 26 ppm, the wastewater treated by the conventional method has a water quality of pH 7.4 and a fluorine concentration of 6.5 pp.
m, COD is 5.7 ppm, PH is 7.6, fluorine concentration is 5.7 ppm, COD is 5.3 ppm, and the generated sludge volume is about 30% or less of the conventional sludge volume. (Embodiment 3) Next, a wastewater treatment process according to an embodiment of the present invention described in claim 6 and an embodiment of the present invention described in claim 7 will be described with reference to FIG.

First, the waste water is transferred to the first reaction adjusting tank 1 as in Example 1, and the calcium carbonate mineral 7 is used to remove and neutralize fluorine. For example, when the amount of air used for aeration is 20 M 3 or more per day per 1 M 3 of water tank capacity, the influent with a fluorine concentration of 120 ppm and a pH of 2.5 is 48 ppm or less at the outlet of the first reaction adjustment tank 1. , PH 4-5
Becomes

Next, the wastewater having a fluorine concentration of 48 ppm is transferred to the second reaction adjusting tank 2 and polyaluminum chloride as an aluminum agent or aluminum sulfate called a sulfuric acid band is added, and the fluorine concentration of the wastewater is reduced to 19.2 ppm. And the PH is 5-7.

Next, the waste water is transferred to the coagulation tank 3 via the sludge immobilization tank 23, and the fine flocs generated in the first and second reaction control tanks 1 and 2 are removed by the polymer coagulant. To grow into large and solid flocks.

Next, the waste water is transferred to the sedimentation tank 4 and subjected to solid-liquid separation using the scraper 13 at a rotation speed of about once every several minutes, and the waste water as a supernatant liquid is discharged to form a precipitate. Unreacted sludge containing aluminum, calcium and fluorine is returned to the sludge fixing tank 23.

Next, the waste water was transferred to the sedimentation tank 4 and subjected to solid-liquid separation using the scraper 13 at a rotation speed of about once every several minutes, and the waste water as a supernatant was discharged to form a precipitate. Unreacted sludge containing aluminum, calcium, and fluorine is transferred to a BSK bacterium or a living system sent from a BSK cultivation tank 25 equipped with a heating device for effectively culturing and a diffuser tube for maintaining aerobicity. Excess sludge and BSK bacteria are mixed in the sludge microorganism mixing tank 26, and the sludge immobilization tank 23
Will be returned to

The sludge return rate is initially set to 100%. However, when the sludge concentration in the sludge fixing tank 23 becomes 4000 ppm or more, in the 100% sludge return rate operation, the wastewater in the flocculation tank 3 and the sedimentation tank 4 Since sludge is mixed into the supernatant, the sludge return rate is reduced to a range where sludge is not mixed into the drainage in the flocculation tank 3 and the supernatant in the sedimentation tank 4.

In this embodiment, the sludge return rate is reduced at a sludge concentration of 3000 ppm or more in the above-described second embodiment, but the operation can be performed at a sludge return rate of 100% until the sludge concentration reaches 4000 ppm. This is because BSK bacteria having adhesiveness to the aggregate (colony) itself are mixed with the returned sludge, so that the sludge can be fixed to the contact material 24 at a higher concentration than in the case of Example 2. is there. At this time, 60% or more of the sludge is adhered and fixed to the contact material 24 made of vinylidene chloride, and anaerobic microorganisms propagate in gaps existing in the contact material 24 to digest the sludge. The amount of sludge is reduced as compared with the case of using.

The removal rate of fluorine in the sludge immobilization tank 23 can be expected to be 70% or more, and the removal rate when organic substances such as surfactants are taken as COD can be expected to be 50% or more.

Next, as in the first embodiment, the sludge is concentrated in the sludge concentration tank 5 and dewatered by the dehydrator 6 to form a dewatered cake.

As described above, if the processing step of Example 3 is used, for example, the first reaction adjusting tank 1 having a capacity of about 5 liters,
When the above steps were carried out using a 2 liter second reaction adjustment tank 2, a sludge immobilization tank 23 having a capacity of about 2.5 liters, and a sedimentation tank having a capacity of about 3 liters, the pH was 2.2 and the fluorine concentration was Is 152 ppm and COD is 41 ppm. When treated wastewater containing fluorine and a surfactant is 41 ppm, the wastewater treated by the conventional method has a pH of 7.3 and a fluorine concentration of 6.8 pp.
m, COD was 6.5 ppm, PH was 7.5, fluorine concentration was 5.1 ppm, COD was 5.2 ppm, and the generated sludge volume was about 20% or less of the conventional sludge. Fourth Embodiment Next, a wastewater treatment process according to an embodiment of the present invention will be described with reference to FIG.

First, the waste water is transferred to the first reaction adjusting tank 1 as in the first embodiment. Here, the amount of water is adjusted so that the calcium carbonate mineral 7 is buried, the fluorine is removed and neutralized by the calcium carbonate mineral 7, and the fluorine concentration is adjusted to 15%.
2020 ppm, PH 4-5. The water temperature at the time of the treatment may be at least 20 ° C., but at least 25 ° C. is effective, and the neutralization treatment is desirably planned in the first half of the wastewater treatment facilities. The reaction time in the first reaction adjustment tank 1 is determined by the concentration of fluorine contained in the wastewater, the inflow amount of the wastewater and the quality of the inflow water, but is considerably longer than in the past, and is usually 10 hours or more. I do. Also,
At the time of the above-described aeration stirring, organic substances such as surfactants in the wastewater are strongly oxidized by the ozone since the aeration is carried out by air containing ozone, and as a result, the value of COD in the wastewater also decreases. .

On the other hand, as a part of the reaction, the dissolved fluorine reacts with the calcium carbonate mineral to change into a calcium fluoride mineral. Here, the air containing ozone is converted into the above-mentioned fluoride. It also catalyzes the conversion to calcium minerals.

The amount of air containing ozone was 1 M in the tank capacity.
It is preferable to design the water tank at a rate of 20M 3 or more per day. The water tank is designed so that the depth of the water tank is aerated with ozone-free air so that the wastewater contacts the ozone-containing air as much as possible. Preferably it is deeper.

Further, in the ozone mixture 32 filled with the filler 33, the air containing ozone is efficiently brought into contact with the drainage gas-liquid.

Next, the waste water immediately after flowing into the first reaction adjusting tank 1 has an acidic pH of 3 or less, so that calcium is ionized while dissolving the calcium carbonate mineral 7,
The above-mentioned fluorine is treated as fine flocs of calcium fluoride, and on the other hand, the fluorine is treated as a calcium fluoride mineral which is a raw material for producing fluorine, so that precipitation of calcium fluoride does not occur, that is, waste as much as possible A system that does not occur.

As described above, in the first reaction adjusting tank 1, the fluorine contained in the waste water is treated by 60% or more, and the oxidation of organic substances by ozone, that is, the removal rate of organic substances such as surfactants and alcohols as COD is reduced. Can be expected to be 20% or more.

Next, the waste water having a fluorine concentration of 15 to 20 ppm and approaching neutrality is transferred to the second reaction adjustment tank 2 and polyaluminum chloride as an aluminum agent and aluminum sulfate called a sulfuric acid band are removed. 500-1000pp
About m is added. In addition, it is preferable to set residence time to 6 hours or more. This aluminum agent reacts with the fluorine contained in the waste water to form aluminum fluoride, and the excess aluminum agent quickly changes into a floc of aluminum hydroxide, adsorbing the aluminum fluoride, reducing the fluorine concentration in the waste water. Reduce to about 5 ppm. It is known that this aluminum hydroxide floc is likely to be generated near neutrality. Also, since the aerated air in the second reaction adjustment tank 2 does not contain ozone, ozone contained in the wastewater of the first reaction adjustment tank 1 is degassed in the second reaction adjustment tank 2 and is removed by ozone. In the processes after the second tank, the influence on the microorganisms existing in each tank is suppressed. Therefore, in addition to the present embodiment, the same effect can be obtained by aerating the first reaction adjusting tank 1 shown in FIGS. 2 and 3 with air containing ozone.

As described above, in the second reaction adjustment tank 2, the fluorine contained in the wastewater can be removed by 60% or more, and when organic substances such as surfactants are taken as COD (Chemical Oxygen Demand), the removal rate is ozone. Although there is an effect on microorganisms, 35% or more can be expected.

Next, the waste water was transferred to the coagulation tank 3, and the fine flocs generated in the first and second reaction control tanks 1 and 2 were added to the polymer coagulant by about several ppm to make them large and firm. Grow to flock. The stirring in the flocculation tank 3 is performed so as not to break the floc.
Slow mechanical agitation is suitable. The reaction time may be about 15 minutes.

Next, the waste water is transferred to the sedimentation tank 4 and subjected to solid-liquid separation using the scraper 13 at a rotational speed of about once every several minutes, and the waste water as a supernatant liquid is discharged to form a precipitate. The sludge is gathered in the sludge thickening tank 5 using the scraper 13, concentrated by sedimentation for 3 hours or more, and then the sludge concentrated by the above treatment is dewatered by the dehydrator 6 such as a filter press. Produce dewatered cake as waste.

As described above, if the processing steps described in Example 4 are used, for example, the first reaction adjustment tank 1 having a capacity of about 5 liters, the second reaction adjustment tank 2 having a capacity of about 5 liters, and the coagulation tank having a capacity of about 1 liter. 3 and a settling tank 4 having a capacity of about 3 liters,
When the above process is carried out, when the wastewater containing fluorine and surfactant having a pH of 2.4, a fluorine concentration of 135 ppm, and a COD of 26 ppm is treated, the water treated by the conventional method has a pH of 7.4. , Fluorine concentration 6.5ppm, COD
Is 5.7 ppm, the PH is 7.1, the fluorine concentration is 5.3 ppm, and the COD is 4.8 ppm, and the generated sludge volume is about 20% or less of the conventional sludge volume.

FIG. 6 is a conceptual diagram of an apparatus for treating fluorine and hydrogen peroxide-containing wastewater (hereinafter referred to as “wastewater”) according to an embodiment of the present invention. In FIG.
Denotes a first reaction adjustment tank. The first reaction adjustment tank 301 is filled with a calcium carbonate mineral 307. Further, the first reaction adjusting tank 301 is provided with a stirrer including two types of diffuser tubes: a diffuser tube 308 and a diffuser tube 331 for stirring calcium carbonate mineral.

The calcium carbonate mineral 307 is filled in a mesh tube 315 provided in the first reaction adjusting tank 301. The mesh tube 315 has a charging cover 320 as an upper portion thereof, a porous plate 333 and a mesh tube air reservoir 316 as lower portions. The perforated plate 333
Has a role of preventing the calcium carbonate mineral 307 from falling from the mesh tube 315.

Of the two types of diffuser tubes 308 and 331, the diffuser tube 308 has a role of stirring the water flow in the first reaction adjusting tank 301 and maintaining dissolved oxygen in the tank. In addition, another diffusing pipe, a diffusing pipe for stirring calcium carbonate mineral 331, stirs the calcium carbonate mineral 307 in the reticulated pipe 315 by air to play a role of positively improving the reaction between fluorine and calcium. Has become. That is, the diffusion pipe 331 for stirring the calcium carbonate mineral has a role of separating the crystalline reactant of calcium fluoride generated on the surface of the calcium carbonate mineral 307 from the surface of the calcium carbonate mineral 307.

On the other hand, the reticulated tube air reservoir 316 prevents the air discharged from the diffusing pipe 331 for agitating the calcium carbonate mineral from jumping out of the reticulated tube 315 to the outside, so that the air can efficiently rise in the reticulated tube 315. It has a role to make.

The two types of air diffusers 308 and 3 shown in FIG.
The stirrer including 31 is an aeration stirrer. This stirring device includes a first-rotation speed control blower 310 and a second rotation speed control blower 310.
A rotation speed control blower 311, a diffuser 308, a diffuser 331 for stirring calcium carbonate minerals, and a control panel 318.
, A PH meter 321, a fluorine meter 332, and a pipe 312 for connecting the rotation speed control blowers 311, 312, the air diffusers 308, 331, and the like. The stirring device may include a mechanical stirrer 13 as shown in FIG. 8 or an underwater stirrer used in water. But,
Stirring by aeration of the air diffuser is more suitable than mechanical stirrer 13 in order to maintain dissolved oxygen in the tank and propagate microorganisms.

When the fluorine concentration in the fluorine-containing wastewater flowing into the first reaction adjusting tank 301 is 50 ppm or less, the pH of the wastewater is often in the range of 3 to 5. In such a case, the amount of stirring air supplied from the air diffusers 308 and 331 may be about 20 M 3 (cubic meters) per day per volume 1 M 3 (cubic meters) of the tank 301. On the other hand, when the fluorine concentration in the fluorine-containing wastewater flowing into the first reaction adjustment tank 301 is 200 ppm or more, the pH of the wastewater is low and often less than 2.5. In such a case, the amount of stirring air supplied from the air diffusers 308 and 331 needs to be 60 M 3 (cubic meters) or more per day per volume 1 M 3 (cubic meters) of the tank 301.

This embodiment uses a PH meter 32 as a detector.
1 and the signal from the fluorine meter 332 are
18 to be transmitted to a controller built in. The controller controls the rotation speeds of the first rotation speed control blower 310 and the second rotation speed control blower 311 so that the air diffusers 331 and 308 supply the tanks 301 and 3.
The amount of air supplied to the tank 02 is optimized, and the insides of the tanks 301 and 302 are stirred with the optimum amount of air.

Therefore, when the above-mentioned fluorine concentration is 50 ppm
In any case of less than or equal to or more than 200 ppm, the amount of air for stirring can be controlled by the PH management by the PH meter 321 and the fluorine concentration management by the fluorine meter 332, and the reaction can be performed effectively. That is, the P measured by the PH meter 321
Based on the H value and the fluorine concentration value measured by the fluorine meter 332, the control panel 318 controls the first rotation speed control blower 310 and the second rotation speed control blower 3
The number of rotations is controlled, and when the fluorine concentration in the wastewater is high and PH is low, the blower is rotated at high speed, and when the fluorine concentration in wastewater is low and PH is high, the blower is rotated at low speed.

In this embodiment, a PH meter 321 and a fluorine meter 3
The attachment position of 32 is at the drain outlet of the first reaction adjustment tank 301. This is because, when the mounting position is set to the drain inlet of the first reaction adjusting tank 301, the fluctuation of the fluorine concentration and the acid concentration of the inflow wastewater flowing into the drain inlet, that is, the fluctuation of PH is larger than the fluctuation at the drain outlet. This is because it is not possible to optimally control and manage the air supply amount. On the other hand, if the attachment position is set at the drain outlet of the second reaction adjustment tank 302, the response of the air amount control may be delayed, and the attachment position may be set at the drain outlet of the first reaction adjustment tank 301. That's why.

The water level in the first reaction adjusting tank 301 is controlled by a pump 309 by a level meter (not shown) for measuring the water level in the tank 301 so that the calcium carbonate mineral 307 is always submerged in the drainage in the tank. Then, the water level of the tank 301 is controlled. Then, as shown in FIG. 7, the amount of water in the tank 301 is adjusted such that the water level of the adjustment tank 301 is always located above the charging cover 320 of the mesh tube 315. Therefore, the input cover 320
Since the lower calcium carbonate mineral 307 is always immersed in the wastewater, the reaction between the fluorine and calcium in the wastewater is promoted.

On the other hand, in the second reaction adjusting tank 302, a mesh tube 315 is filled with a calcium carbonate mineral 307 and activated carbon 334. Further, the tank 302 contains an aluminum agent.
(Not shown). In addition, the second reaction adjustment tank 302 is provided with 2
Different types of air diffusers 308 and 331 are provided.

The calcium carbonate mineral 307 used in the above embodiment of the present invention is obtained by pulverizing natural limestone, and also exists as heavy calcium carbonate and cold water stone (trade name). In addition, since the aqueous solution of slaked lime is strongly alkaline, the aqueous solution of naturally occurring calcium carbonate mineral shows neutrality. Therefore, it is necessary to breed small fish such as medaka and locust in the above aqueous solution of calcium carbonate mineral. Can be. The calcium carbonate mineral is a chemically safe substance, and the surface thereof is uneven, so that microorganisms can easily propagate. Therefore, the presence of the calcium carbonate mineral 307 makes it easier to treat the organic matter in the wastewater.

The particle size of the calcium carbonate mineral 307 filled in the mesh tube 315 provided in the first reaction adjusting tank 301 is larger than the particle size of the calcium carbonate mineral 307 filled in the second reaction adjusting tank 302. You have set. This is because the first wastewater in the first reaction adjustment tank 302 has an acidic pH of 3 or less, and in order to react with the acidic wastewater having a pH of 3 or less, it is preferable that the calcium carbonate mineral 307 has a coarse particle size. Because it is suitable. Specifically, the particle size of the calcium carbonate mineral 307 in the first reaction adjustment tank 301 is set to about 1 to 1.5 cm in diameter, and the particle size of the calcium carbonate mineral 307 in the second reaction adjustment tank 302 is set to 0 It was about 0.5 to 1 cm, but this is not an absolute condition. Since the calcium carbonate mineral 307 having a particle size of about 1 cm easily dances by the air stirring and the aeration by the air diffuser 308 and the air diffuser 331, effective stirring can be realized, and the reaction between fluorine and calcium is effectively performed. Done.

The type of the activated carbon 334 filled in the lower part of the mesh tube 315 provided in the second reaction adjusting tank 302 is not particularly limited, and may be a coconut shell type or a coal type. As for the size of the calcium carbonate mineral to be selected, a commercially available product having a particle size of 5 to 10 mm may be selected. In short, the activated carbon 334 is transferred from the mesh tube 315 to
It is good not to spill. Further, when the wastewater is passed through the activated carbon 334, the pH of the wastewater tends to increase. Specifically, the activated carbon 334 is a substance that acts on the alkali side, and is therefore more convenient particularly for treating fluorine-containing wastewater having a low PH. In addition, activated carbon is
Because it is porous and microorganisms can easily propagate in the pores,
Suitable as a carrier for immobilizing microorganisms.

Further, the second reaction adjusting tank 3 is used as a coagulant.
The aluminum agent added to 02 effectively removes wastewater in the tank 302. Here, the fluorine concentration in the wastewater in the tank 302 is 15 to 20 ppm or less, and the wastewater is sufficiently aerated. Further, as the wastewater is closer to neutral, the wastewater by the aluminum agent becomes more neutral. Empirical evidence has shown that fluorine removal is effective. Therefore, in this embodiment, in the first reaction adjustment tank 301,
The waste water is first reacted with the calcium carbonate mineral 307 to reduce the fluorine concentration at the outlet of the first
It is adjusted to about 20 ppm, and it approaches neutrality while aerating. Thereafter, in order to further remove fluorine in the next step, an aluminum agent is added as a coagulant in the second reaction adjusting tank 302 to reduce the fluorine concentration of the wastewater to about 3 ppm.

Further, an inorganic coagulant such as an aluminum agent and a polymer coagulant can be added to the coagulation tank 303 of this embodiment. Further, the sedimentation tank 30 of this embodiment
In 4, the solid-liquid separation of the wastewater is performed. In FIG. 6, reference numeral 305 denotes a sludge thickening tank; 306, a dehydrator such as a filter press; 313, a stirrer;
14 is a scraper.

In the wastewater treatment apparatus of this embodiment, the first reaction adjusting tank 301 corresponding to the conventional raw water tank 14 is filled with the calcium carbonate mineral 307, and the adjusting tanks 301, 3
02, a diffuser 308 as a stirring means and an aeration means,
331 or a mechanical stirrer such as an underwater stirrer is provided. Therefore, according to this embodiment, the wastewater is neutralized by the first reaction adjustment tank 301,
By reacting the fluorine contained in the wastewater with the calcium carbonate mineral 307, a treatment for reducing the fluorine concentration of the wastewater can be performed. Therefore, according to the above embodiment, the number of man-hours for managing and managing chemicals, which has been a problem in the past, can be reduced with a simple overall configuration. That is, according to the present embodiment, the mechanical management scale of the wastewater treatment apparatus can be significantly reduced compared to the related art, and the maintenance cost of the equipment can be reduced. Further, in this embodiment, the mechanical management scale of the wastewater treatment apparatus is reduced as compared with the related art, and the embodiment has an organic matter treatment function not provided in the conventional wastewater treatment equipment.

As described above, as the stirring means in the above embodiment, it is more preferable to use an aeration apparatus for making the inside of the tank an aerobic atmosphere than using mechanical stirring means. Aerobic microorganisms can easily treat organic matter in wastewater.

Next, a method for treating wastewater containing fluorine and hydrogen peroxide (hydrogen peroxide) according to one embodiment of the present invention will be described.
This will be described with reference to FIG. This embodiment corresponds to FIG.
This is performed using the wastewater treatment device shown in FIG.

First, the fluorine concentration is 30 to 3 depending on the time.
Fluorine- and peroxide-containing wastewater (hereinafter referred to as “wastewater”) that varies in the range of 00 ppm and the concentration of peroxide varies with time in the range of 10 to 50 ppm is the first reaction adjustment tank 301.
Transfer to

Here, the discharge water amount of the pump 309 and the control water level are adjusted so that the calcium carbonate mineral 307 provided in the first reaction adjusting tank 301 is always buried in the wastewater. Then, in the first reaction adjustment tank 301, the removal and neutralization of fluorine in the wastewater by the calcium carbonate mineral 307 are performed. The above treatment can be carried out at a waste water temperature of 20 ° C. or more, and most preferably, about 30 to 40 ° C.

At the drain outlet of the first reaction adjusting tank 301,
The reaction time in the first reaction adjustment tank 301 is sufficiently set so that the fluorine concentration of the wastewater is 15 to 20 ppm, and the reaction is performed while stirring and agitating the inside of the tank 301 strongly. To do.

When the capacity of the first reaction adjusting tank 301 is 240
Liter, and when the inflow concentration of fluorine due to the inflow of the wastewater is 120 ppm, the first reaction adjustment tank 3
The fluorine concentration of the wastewater can be adjusted to 15 to 20 ppm by the wastewater residence time within about 3 hours in the wastewater. The reaction time in the first reaction adjustment tank 301 is determined by the concentration of fluorine and the concentration of acid contained in the wastewater and the amount of aerated air. According to the experimental example, a residence time of 3 hours or more in the first reaction adjustment tank 301 is sufficient.

On the other hand, the air diffusers 308 and 33
At the time of aeration and stirring by the method (1), microorganisms existing in the air are mixed into the drainage in the tank. Regarding the contamination of the microorganisms, the second reaction adjusting tank 302 is particularly more suitable for the first reaction adjusting tank 3.
Although the conditions are better than 01, the microorganisms grow on the surfaces of the calcium carbonate mineral 307 and the activated carbon 334 in each tank. And the said drainage is made near neutral also by the buffer action of those microorganisms.

The effluent immediately after flowing into the first reaction adjusting tank 301 is acidic with a pH of 3 or less. Therefore, the effluent dissolves the calcium carbonate mineral 307 in the tank 301 to ionize calcium, The fluorine in the wastewater is treated as fine flocs of calcium fluoride and crystalline reactants. Then, carbon dioxide gas and water are generated as a result of the processing.

Conventionally, excess slaked lime (Ca (OH) 2 ) has been added to wastewater in order to treat fluorine in the wastewater, so that a large amount of hydroxide derived from slaked lime has been generated. However, in the embodiment of the present invention, a reaction between fluorine and calcium can be caused according to a chemical reaction formula.
Therefore, according to this embodiment, there is no generation of the hydroxide, and the amount of generation of sludge is remarkably reduced as compared with the conventional example.

In the first reaction adjusting tank 301, the waste water having a fluorine concentration of 15 to 20 ppm and a neutral water concentration of 10 to 50 ppm is then discharged to the pipe 12.
Then, the mixture is transferred to the second reaction adjusting tank 302 via the pump 309, and polyaluminum chloride or a sulfuric acid band as an aluminum agent is added to the second reaction adjusting tank 302. Then, the aluminum agent reacts with the fluorine in the waste water to produce aluminum fluoride. In addition, the excess aluminum agent quickly changes into a floc of aluminum hydroxide, and adsorbs the aluminum fluoride. This allows
The fluorine concentration of the wastewater can be reduced to 3 ppm or less.

It is known that the above flocs of aluminum hydroxide are more likely to be generated near neutrality than in acidic conditions.
Conventionally, the pH of the wastewater decreases when the acidic chemical, which is the above-mentioned aluminum agent, is added to the wastewater. Therefore, an alkaline chemical such as caustic soda is added to the wastewater to neutralize the wastewater. On the other hand, in this embodiment, the calcium carbonate mineral 307 provided in the first reaction adjustment tank 301 and the second reaction adjustment tank 3
02, the wastewater is neutralized by the calcium carbonate mineral 307 and the calcium carbonate mineral 307 and the activated carbon 3
The wastewater is automatically and safely neutralized by microorganisms from the air growing on the surface. Therefore, according to this embodiment, the conventionally required PH adjustment tank becomes unnecessary. Also, in this embodiment, when the fluorine concentration in the wastewater rises, the diffuser tubes 308 and 33 are automatically increased as compared with the normal case.
Calcium carbonate mineral 307
The microorganisms immobilized on the surface are peeled off, and fluorine is treated by the cohesiveness of the flocs of the peeled microorganisms. This can further reduce the amount of the aluminum agent used.

Next, the waste water is transferred from the second reaction adjustment tank 302 to the coagulation tank 303, and the first and second reaction adjustment tanks
The fine flocs and microbial flocs generated in steps 01 and 302 are grown into large and firm flocs by a polymer flocculant. The stirring of the flocculant 303 by the stirrer 313 is preferably performed by slow mechanical stirring at about 30 rpm so as not to break the floc. According to this example, the amount of the polymer flocculant used could be reduced by about 30% as compared with the conventional example.

Next, the waste water is transferred from the flocculation tank 303 to the precipitation tank 304, and the waste water is subjected to solid-liquid separation using a scraper 314. The supernatant of the wastewater is transferred to the precipitation tank 304.
Release from On the other hand, the sludge formed by settling in the settling tank 304 is sent to the sludge thickening tank 305,
At 05, it is scraped using scraper 314 and concentrated by sedimentation.

Next, the sludge concentrated by the above treatment is transferred from the sludge concentration tank 305 to a dehydrator 306 including a filter press and the like, and the sludge is dehydrated by the dehydrator 306 to obtain a dewatered cake as industrial waste. Generate

Next, in order to compare the above-described embodiment with the conventional example, the experimental results obtained by the experimental apparatus of the above-described embodiment shown in FIG. 6 are shown below.

In the experimental apparatus corresponding to the above embodiment, the first
The capacity of the reaction adjustment tank 301 was set to 240 liters, and the capacity of the second reaction adjustment tank 302 was set to 200 liters. An experiment was conducted according to the processing flow shown in FIG. On the other hand, with respect to the conventional example, an experiment was conducted with the content of the flow based on FIG.

1) Water quality PH of raw water of fluorine-containing wastewater 2.3 Fluorine concentration 152 ppm COD 18 ppm Hydrogen peroxide concentration 32 ppm 2) Water quality PH 7.2 of treated water by an experimental apparatus corresponding to the above embodiment shown in FIG. Fluorine concentration 1.2 ppm COD 4.2 ppm Hydrogen peroxide concentration 1 ppm or less 3) Water quality of treated water by an experimental device corresponding to the conventional example shown in FIG. 7 PH 7.7 Fluorine concentration 6.2 ppm COD 16 ppm Hydrogen peroxide concentration 28 ppm 4) Sludge generation amount When the amount of sludge generation was measured in the above experiment, the amount of sludge generated from the experimental device of the above embodiment was about the amount of sludge generated from the experimental device corresponding to the conventional example shown in FIG. It was less than 20%.

In the above embodiment of the invention according to claims 18 and 15 corresponding to FIG.
Calcium carbonate mineral 3 without filling activated carbon 334
7 corresponding to FIG. 5 when only 07 is filled.
Embodiments of the invention described in 3, 10 are realized. That is, the difference between the embodiment corresponding to FIG. 6 and the embodiment corresponding to FIG. 5 is whether or not the second reaction adjustment tank is filled with activated carbon.

[0160]

As described in detail above, claims 1 to 5
By using the invention described in Item 8, the following effects can be obtained.

First, in a raw water tank that was conventionally provided only for adjusting the amount of water and the quality of the water, the fluorine was removed with calcium carbonate and the waste water was neutralized, and a sufficient reaction time was taken to avoid excessive chemicals. Therefore, the running cost such as the chemical cost is reduced, and the hydroxide, which has been a large part of the conventional sludge, is not generated. Therefore, the amount of the generated sludge is reduced, whereby the PH as shown in FIGS. 8 and 9 is reduced. Adjustment tank 22
Need not be provided, and the size of apparatuses such as a flocculation tank, a sedimentation tank, and a stirrer can be reduced.

At the same time as the removal of fluorine, the microorganisms propagated on the calcium carbonate mineral and the BSK bacteria can be used to remove biological substances such as surfactants without planning a biological treatment facility capable of newly adding nutrients to the microorganisms. Processing becomes possible, and the amount of waste is significantly reduced.

In addition, surplus sludge for domestic use which requires treatment costs can be effectively used as a nutrient for microorganisms for wastewater treatment, and
The generation of new excess sludge is small due to the digestion of the excess sludge, and the amount of waste can be reduced.

Furthermore, by using aeration with air containing ozone, fluorine and organic substances can be treated stably and efficiently in the same water tank at the same time, so that the processing system is simpler than the conventional method as a whole system. Therefore, the number of tanks can be reduced, and the number of mechanical equipments attached to these tanks is small, which helps to reduce the initial cost.

Further, the wastewater treatment apparatus according to the ninth aspect of the present invention has a wastewater introduction means for introducing wastewater and a stirring means capable of adjusting the stirring intensity, and has a filling section filled with calcium carbonate mineral in advance. Since the first water tank is provided, the fluorine contained in the wastewater reacts with the calcium carbonate mineral, and the fluorine in the wastewater is treated. Further, since the crystalline reactant of calcium fluoride generated on the surface of the calcium carbonate mineral is separated from the surface of the calcium carbonate mineral by the stirring of the stirring means, the reaction between the calcium carbonate mineral and the fluorine is performed. Is promoted, and the fluorine treatment can be performed efficiently. In addition, since microorganisms are easily generated on the surface of the calcium carbonate mineral, the calcium carbonate mineral serves as a carrier for immobilizing the microorganism. Then, the microorganisms eat fluorine in the wastewater and concentrate in the body. In particular, when a microorganism having a remarkable ability to accumulate fluorine in the body is found in the future, by utilizing the microorganism, the processing ability of fluorine is remarkably improved.

[0166] The effluent treatment device according to claim 9 is
Further, in the second water tank, an aluminum agent is added to the wastewater,
The aluminum agent reacts with the fluorine contained in the waste water to produce aluminum fluoride. Further, aluminum hydroxide is generated from the aluminum agent, the aluminum hydroxide is flocculated, and the aluminum fluoride floc adsorbs the aluminum fluoride by the adsorption action of the aluminum hydroxide floc. Also in this second water tank, the treatment of fluorine by the calcium carbonate mineral and the microorganisms inhabiting the calcium carbonate mineral further proceeds.

According to the wastewater treatment method of the present invention, the above wastewater treatment is performed, the fluorine concentration of the wastewater is reduced to a predetermined value, and the PH value of the wastewater is reduced.
The value is set within a predetermined range close to neutrality.

[0168] According to the wastewater treatment apparatus of the eleventh aspect of the present invention, there is provided a mesh pipe for storing the calcium carbonate mineral, and the lower portion of the mesh pipe is an unfilled air reservoir. If air is supplied from below, the calcium carbonate mineral is efficiently supplied with air. Therefore, microorganisms derived from the air can easily propagate in the calcium carbonate mineral, and the efficiency of wastewater treatment by the microorganisms can be improved.

According to the twelfth aspect of the present invention,
Since the stirring means includes aeration means including a diffuser tube, the supply of air from the diffuser tube agitates drainage in a water tank provided with the mesh pipe, and makes the inside of the tank aerobic. Therefore, the aerobic microorganisms can easily treat the organic matter in the wastewater, and the efficiency of the wastewater treatment can be improved.

The wastewater treatment apparatus according to the thirteenth aspect measures the PH value of the wastewater and the fluorine concentration of the wastewater, and outputs the aeration output of the stirring means based on the PH value and the fluorine concentration. , The wastewater treatment capacity can be optimally controlled according to the wastewater.

Further, according to the wastewater treatment apparatus of the present invention, since the second water tank is filled with activated carbon in addition to the calcium carbonate mineral, the above-mentioned effect of the invention of claim 11 is obtained. In addition to the above, the activated carbon has an effect of decomposing hydrogen peroxide in wastewater. Therefore, according to the fourteenth aspect, wastewater containing fluorine and hydrogen peroxide can be treated simultaneously.

According to the wastewater treatment method of the present invention, the calcium carbonate mineral and the aluminum agent treat fluorine in the wastewater, and the activated carbon removes hydrogen peroxide in the wastewater. By performing the treatment, the fluorine concentration and the hydrogen peroxide concentration in the wastewater can be reduced to predetermined values, and the PH value in the wastewater can be set to a value in a predetermined range.

In the wastewater treatment apparatus according to the present invention, the first water tank has a mesh tube filled with a calcium carbonate mineral, and the second water tank has a mesh tube filled with a calcium carbonate mineral and activated carbon. Since the lower space of the mesh tube is a non-filled air reservoir, the air is efficiently supplied to the calcium carbonate mineral by supplying air from the lower portion of the mesh tube. Therefore, microorganisms derived from the air can easily propagate in the calcium carbonate mineral, and the efficiency of wastewater treatment by microorganisms can be improved. Further, in the second water tank, since air is efficiently supplied not only to the calcium carbonate mineral but also to the activated carbon, microorganisms derived from the air easily propagate in the activated carbon, and the efficiency of wastewater treatment by microorganisms is reduced. Can be improved.

In the wastewater treatment apparatus according to the seventeenth aspect of the present invention, since the stirring means includes aeration means including a diffuser, the water tank provided with the mesh pipe is supplied by the supply of air from the diffuser. The internal drainage is stirred, and the inside of the tank becomes aerobic. Therefore, the aerobic microorganisms can easily treat the organic matter in the wastewater, and the efficiency of the wastewater treatment can be improved.

According to the wastewater treatment apparatus of the present invention, the PH value of the wastewater and the fluorine concentration of the wastewater are measured, and based on the PH value and the fluorine concentration, the agitation of the stirring means is performed. Since the aeration output is controlled, according to the above drainage,
Wastewater treatment capacity can be optimally controlled.

As described above, in the inventions of claims 9 to 18, the removal of fluorine by calcium carbonate and the neutralization of wastewater are performed in place of the raw water tank in which the water amount and the water quality are only adjusted conventionally. Since the first water tank is used, the size of the wastewater treatment device can be reduced. In addition, since excess chemicals are not used, and hydroxide, which is a large part of the conventional sludge, is not generated, the amount of sludge generated from the wastewater treatment device is significantly reduced. , And a device such as a stirrer can be reduced in size. As described above, the entire apparatus is simplified, the operation management of the apparatus is facilitated, and the initial cost and the running cost can be reduced.

[0177] At the same time as effective fluoride and water removal, microorganisms propagated on calcium carbonate minerals
Biological treatment of organic substances such as surfactants and alcohol in wastewater can be performed. As described above, the present invention can provide a resource-saving, energy-saving, and environmentally friendly wastewater treatment system in an era when the global environment is to be preserved.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram of a wastewater treatment apparatus containing fluorine and a surfactant according to an embodiment of the present invention described in claims 1 and 3.

FIG. 2 is a conceptual diagram of a wastewater treatment apparatus containing fluorine and a surfactant according to an embodiment of the present invention described in claim 5;

FIG. 3 is a conceptual diagram of an apparatus for treating wastewater containing fluorine and a surfactant according to one embodiment of the present invention described in claims 6 and 7;

FIG. 4 is a conceptual view of a wastewater treatment apparatus containing fluorine and a surfactant according to an embodiment of the present invention described in claim 8;

FIG. 5 is a system diagram for explaining an embodiment of a wastewater treatment apparatus according to the invention of claim 13 and a wastewater treatment method of the invention according to claim 10;

FIG. 6 is a system diagram illustrating an embodiment of a wastewater treatment apparatus according to the invention of claim 18 and a wastewater treatment method of the invention according to claim 15.

FIG. 7 is a system diagram illustrating a conventional wastewater treatment apparatus and a conventional wastewater treatment method.

FIG. 8 is a system diagram illustrating a wastewater treatment apparatus and a wastewater treatment method including conventional biological treatment means.

FIG. 9 is a conceptual diagram of a conventional wastewater treatment apparatus for treating hydrogen peroxide-containing wastewater.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... 1st reaction adjustment tank, 2 ... 2nd reaction adjustment tank, 3 ... Coagulation tank, 4 ... Sedimentation tank, 5 ... Sludge concentration tank, 6 ... Dehydrator, 7 ... Calcium carbonate mineral, 8 ... Aeration tube, 9 ... Pump: 10 blower, 11: piping, 12: stirrer, 13: scraper, 23: sludge fixing tank, 24: contact material, 25: BSK bacteria culture tank, 26: sludge microorganism mixing tank, 27
... Heating device 28 ... Contact oxidation tank, 29 ... Filter medium, 30 ... Ozone generator,
Reference Signs List 31: Filter 32: Ozone mixing unit, 33: Filler, 201, 301: First reaction adjustment tank, 202, 302: Second reaction adjustment tank, 203, 303: Aggregation tank, 204, 304: Precipitation tank, 205, 305: sludge thickening tank, 206, 306: dehydrator, 207, 307: calcium carbonate mineral, 208, 308
... diffuser tubes, 209, 309 ... pumps, 210, 310 ... first blowers, 211, 311 ... second blowers, 212, 312 ... pipes, 213, 313 ... stirrers, 214, 314 ... scrapers, 215, 315 ... Reticulated tube, 216, 316: Reticulated tube air reservoir, 217, 317: Inclined wall, 218, 318: Control panel, 219, 319: Electric wiring, 220, 320: Input cover, 221, 321: PH meter, 222, 322 ... raw water tank, 223,323 ... first reaction tank, 224,324 ... second reaction tank, 225,325 ... first flocculation tank, 226,326 ... first precipitation tank, 227,327 ... third reaction tank, 228 , 328: second coagulation tank, 229, 329: second precipitation tank, 230, 330: PH adjustment tank, 231, 331: diffuser pipe for stirring calcium carbonate mineral, 232, 332 ... Fluorine meter, 233,333 ... Perforated plate,
334 ... Activated carbon.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. 6 Identification code FI C02F 9/00 501 C02F 9/00 501Z 502 502P 503 503Z 504 504A ZAB ZAB (31) Priority claim number Japanese Patent Application No. 5-86996 ( 32) Priority Date Hei 5 (1993) April 14 (33) Priority Country Japan (JP) (72) Inventor Shunji 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Corporation (72) Invention Kazuyuki Sakata 22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka Inside Sharp Corporation (72) Inventor Takashi Imai 22-22-22 Nagaikecho, Abeno-ku, Osaka City, Osaka Prefecture Sharp Corporation (72) Inventor Shigetoshi Okaya Osaka Prefecture 22-22, Nagaikecho, Abeno-ku, Osaka Sharp Corporation (72) Inventor Satoshi Nishio 22-22, Nagaikecho, Abeno-ku, Osaka-shi, Osaka (72) Inventor Tsuyoshi Takahashi 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Sharp Corporation (72) Inventor Kenji Matsuura 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Sharp Corporation (72 Inventor Noriyuki Tanaka 22-22 Nagaikecho, Abeno-ku, Osaka-shi, Osaka Inside Sharp Corporation (72) Inventor Teruro Nagai 22-22 Nagaikecho, Abeno-ku, Osaka-shi Osaka Prefecture Inside Sharp Corporation (56) References JP 54-7762 (JP, A) JP-A-50-127772 (JP, A) JP-A-54-144765 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C02F 1/58 C02F 3/06 C02F 3/10 C02F 3/34 C02F 9/00

Claims (18)

    (57) [Claims]
  1. A first water tank filled with a calcium carbonate mineral, a means for introducing waste water containing fluorine, and a means for introducing waste water treated by the first water tank; A wastewater treatment apparatus, comprising: a second water tank having means, an aluminum agent added, and a calcium carbonate mineral.
  2. 2. While stirring waste water containing fluorine,
    A step of reacting the wastewater with calcium carbonate in the first water tank filled with a calcium carbonate mineral to reduce the fluorine concentration of the wastewater to a predetermined value; while stirring the wastewater treated in the step, In the second water tank to which the aluminum agent is added and filled with the calcium carbonate mineral, the waste water is reacted with the aluminum agent and the calcium carbonate mineral to reduce the fluorine concentration of the waste water to a predetermined value, and to reduce PH. A step of setting a value within a predetermined range.
  3. 3. A means for introducing wastewater containing fluorine and organic matter and means for stirring, a first water tank filled with calcium carbonate mineral, and means for introducing wastewater treated by the first water tank. A second water tank to which an aluminum agent is added and filled with a calcium carbonate mineral; a means for introducing wastewater treated by the second water tank; and a means for stirring. A third water tank to which a molecular coagulant has been added, a fourth water tank having a means for solid-liquid separating wastewater from the third water tank and discharging an overhead liquid, and a sludge precipitated in the fourth water tank. A wastewater treatment apparatus comprising: a fifth water tank for concentrating by sedimentation and separation; and a dewatering device for dewatering sludge concentrated in the fifth water tank.
  4. 4. The wastewater containing fluorine and an organic substance is stirred while the wastewater and calcium carbonate are reacted in the first water tank filled with a calcium carbonate mineral, and the fluorine concentration of the wastewater is set to a predetermined value. And agitating the wastewater treated in the step, reacting the wastewater with the aluminum agent and the calcium carbonate mineral in the second water tank to which the aluminum agent was added and filled with the calcium carbonate mineral. Reducing the fluorine concentration of the wastewater to a predetermined value,
    And a step of setting the PH to a value within a predetermined range, a step of concentrating the sludge generated in the step by sedimentation and separation, and a step of dewatering the sludge concentrated in the step. Method.
  5. 5. A sixth water tank having a means for introducing wastewater from the second water tank and leading the wastewater to the third water tank and a sludge fixing means, and a sludge formed in the fourth water tank. The wastewater treatment apparatus according to claim 3, further comprising a transport unit configured to transport the wastewater to the fifth water tank or the sixth water tank.
  6. 6. The Bacillus subtilis.
    The wastewater treatment apparatus according to claim 5, further comprising a unit for introducing Kubota bacteria.
  7. 7. The wastewater treatment apparatus according to claim 6, further comprising means for introducing the Bacillus subtilis kubota bacterium and surplus sludge for living use into the sixth water tank.
  8. 8. The agitating means provided in the first water tank is aeration stirring using air containing ozone, and the agitating means provided in the second water tank is used for agitating air using ozone-free air. The wastewater treatment device according to any one of claims 1, 3, 5, 6, and 7, wherein the wastewater treatment device is agitated by air.
  9. 9. A first water tank having a wastewater introducing means for introducing wastewater, a stirring means for stirring the wastewater and adjusting the stirring power to be strong and weak, and a filling part filled with calcium carbonate mineral. A drainage introducing means for introducing wastewater from the first water tank, a stirring means for stirring the wastewater, the stirring power of which is adjusted to be strong and weak, and a filling portion filled with calcium carbonate mineral; A wastewater treatment device, comprising: a second water tank to be added.
  10. 10. A first material filled with a calcium carbonate mineral.
    A step of introducing wastewater into a water tank; a step of causing the wastewater to react with the calcium carbonate mineral in the first water tank to reduce the fluorine concentration of the wastewater to a predetermined value; And introducing the mixture into a second water tank filled with a calcium carbonate mineral, and adding an aluminum agent while stirring the wastewater in the second water tank, and adding the aluminum agent and the carbonate in the second water tank. Calcium mineral, reacting the wastewater, and, when aerating the calcium carbonate mineral, microorganisms that peel off from the calcium carbonate mineral, and reacting the wastewater, further coagulating the reaction product, Reducing the fluorine concentration of the wastewater to a predetermined value and setting the PH value of the wastewater to a value within a predetermined range.
  11. 11. The wastewater treatment apparatus according to claim 9, wherein the first water tank and the second water tank include a perforated plate that partitions a space in the pipe into an upper part and a lower part, and the pipe wall has a mesh shape. A wastewater treatment apparatus comprising a tube, wherein an upper space of the mesh tube is filled with a calcium carbonate mineral, and a lower space of the mesh tube is an unfilled air reservoir.
  12. 12. The wastewater treatment apparatus according to claim 9, wherein said stirring means includes aeration means including an air diffuser.
  13. 13. The drainage treatment apparatus according to claim 12, wherein the pH of the wastewater introduced from the first water tank to the second water tank is adjusted.
    It has a PH meter for measuring the value and a fluorine concentration meter for measuring the fluorine concentration of the wastewater, based on the PH value measured by the PH meter and the fluorine concentration measured by the fluorine concentration meter,
    A wastewater treatment apparatus comprising aeration output control means for controlling the aeration output of the aeration means of the stirring means.
  14. 14. A first water tank having a wastewater introduction means for introducing wastewater, a stirring means for stirring the wastewater and adjusting the stirring power to be strong and weak, and a filling section filled with calcium carbonate mineral. A wastewater introducing means for introducing wastewater from the first water tank, a stirring means for stirring the wastewater, the stirring power of which is adjusted to be strong and weak, and a filling section filled with calcium carbonate mineral and activated carbon; A second water tank to which an agent is added.
  15. 15. A first material filled with a calcium carbonate mineral.
    A step of introducing wastewater into a water tank; a step of causing the wastewater to react with the calcium carbonate mineral in the first water tank to reduce the fluorine concentration of the wastewater to a predetermined value; From the step of introducing into a second water tank filled with calcium carbonate mineral and activated carbon, while stirring the wastewater in the second water tank, adding an aluminum agent, in the second water tank, the aluminum agent and The calcium carbonate mineral and the activated carbon are reacted with the wastewater, and the microorganisms that separate from the calcium carbonate mineral and the activated carbon when the calcium carbonate mineral and the activated carbon are aerated, and the wastewater are further reacted. Aggregating the reaction product, reducing the fluorine concentration and hydrogen peroxide concentration of the wastewater to a predetermined value, and setting the PH value of the wastewater to a value within a predetermined range; Waste water treatment method characterized in that it comprises.
  16. 16. The wastewater treatment apparatus according to claim 14, wherein the first water tank and the second water tank include a perforated plate that partitions an inner space of the pipe into an upper part and a lower part, and the pipe wall has a mesh shape. An upper space of the reticulated tube of the first water tank is filled with a calcium carbonate mineral; a lower space of the reticulated tube is an unfilled air reservoir; A wastewater treatment apparatus, wherein an upper space of a mesh tube of a water tank is filled with a calcium carbonate mineral and activated carbon, and a lower space of the mesh tube is an unfilled air reservoir.
  17. 17. The wastewater treatment apparatus according to claim 14, wherein said stirring means includes aeration means including an air diffuser.
  18. 18. The drainage treatment device according to claim 17, wherein the pH of the wastewater introduced from the first water tank to the second water tank is adjusted.
    It has a PH meter for measuring the value and a fluorine concentration meter for measuring the fluorine concentration of the wastewater, based on the PH value measured by the PH meter and the fluorine concentration measured by the fluorine concentration meter,
    A wastewater treatment apparatus comprising aeration output control means for controlling the aeration output of the aeration means of the stirring means.
JP14934993A 1992-07-31 1993-06-21 Wastewater treatment device and wastewater treatment method Expired - Fee Related JP2812640B2 (en)

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JP20505692 1992-07-31
JP31339392 1992-11-24
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JP4-313393 1993-04-14
JP4-205056 1993-04-14
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JP14934993A JP2812640B2 (en) 1992-07-31 1993-06-21 Wastewater treatment device and wastewater treatment method
US08/097,857 US5480537A (en) 1992-07-31 1993-07-29 Apparatus for waste water treatment using calcium carbonate mineral and microorganisms in combination
US08/452,400 US5580458A (en) 1992-07-31 1995-05-26 Method for waste water treatment using calcium carbonate mineral and microorganisms in combination

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